Distal Amidoketone Synthesis Enabled by Dimethyl Benziodoxoles via Dual Copper/Photoredox Catalysis

Herein, we report distal amidoketone and nitrogen-functionalized ketone syntheses from alcohols and N–H nucleophiles enabled by hypervalent iodine dimethyl benziodoxoles, BIm. Dimethyl benziodoxoles BIm dually activate alcohols and various N–H nucleophiles by forming key BIm–O and BIm–N complexes in which the BIm–N complex is characterized by X-ray crystallography and computationally investigated. Readily available N–H nucleophile imides, sulfonamides, carbamates, triazoles, indazoles, and sulfoximines engage in photoredox/copper catalysis to synthesize distal amidoketones and nitrogen-functionalized ketones with excellent regioselectivity and chemoselectivity. This reaction scales up to grams, applies to late-stage complex molecule modification, and streamlines synthetic routes.